TW200540263A - Process for washing - Google Patents

Abstract

A method of improving smoothness during washing of an item to be washed, including the step of washing the item with a washing liquid under conditions where an organic polymer having spinnability is present in the washing liquid; a process for hand-washing including the step of hand-washing an item to be washed with a washing liquid showing spinnability containing an organic polymer having spinnability, or a washing liquid prepared by diluting the washing liquid with more than 1-fold to 1,000-fold amount of water; a detergent composition containing an organic polymer having spinnability having an average molecular weight of 1,500,000 or more in an amount exceeding 0.1% by weight of the detergent composition; a laundry detergent composition comprising a polymer having an average molecular weight of 500,000 or more, wherein 60% by mole or more of constituting monomers has a sulfonic acid group or a salt form thereof, or a sulfuric acid group or a salt form thereof. The detergent composition of the present invention can be especially suitably used in hand-washing.

Description

200540263 IX. Description of the invention: [Technical field to which the invention belongs] The present invention relates to a method for improving the sliding property of a material to be washed, a hand washing method, a detergent composition, a detergent composition for clothes, and a sliding property improving agent. The present invention also relates to a washing method using the above-mentioned detergent composition, a laundry detergent composition, or a slip improver. [Prior art] As washing methods, there are roughly two types of washing methods: hand washing and washing machine washing. In recent years, due to the popularity of washing machines, washing machine washing tends to increase, but hand washing is still used in consideration of fouling removal or economical aspects. / Hand washing and washing, compared with washing machine washing, it can achieve a slight washing according to the condition of dirt removal, the type of objects to be washed, etc., but it can cause physical and mental fatigue to the washing person. In particular, the "hand rubbing" of rubbing the objects to be washed each other is the most natural hand-washing method that is easy to apply mechanical force to the part being washed, but long-term operation will cause a few dollars to the person who cleans it. It is not smooth, and resistance will be generated when rubbing the objects to be washed. This resistance is an unpleasant factor of "coarse =" and "friction" which brings unpleasant sensation to the cleansing person, and the physical exertion caused by the movement is examined, and the post-coupling will also add more burden to the body. In addition, the local, s μ-thick rubbing that occurs during hand rubbing can cause hand abrasions and cuts to humans, and cause fibers to be washed. The damage of 99474.doc 200540263 of fiber not only shortens the durability period of clothes, but also promotes the adhesion of dirt, and further increases the physical burden required for washing. In addition, this frictional resistance may cause fiber damage or aliasing due to mechanical forces such as stirring when washing the washing machine. On the other hand, the previous focus was on improving the detergency of detergents or preventing recontamination of clothes and laundry, such as the so-called "how to remove the attached dirt from the laundry", or on the clothes after washing. Development of so-called "retouching clothes after washing", such as imparting flexibility (for example, refer to Japanese Patent Publication No. Hei 5-508889, Japanese Patent No. 26203 18, Japanese Patent Laid-Open No. 7-216389), So far, no technology has been developed that takes into account the unpleasant factors or physical loads generated by the above-mentioned hand washing and washing, that is, "brings mental and physical burden to the washing person" and focuses on the improvement. [Summary of the invention] That is, the gist of the present invention is about [U—a method for improving the sliding property of a washed object in a washing liquid, which is to make a stringy organic polymer exist in the washing liquid during washing; [2] — A method for improving the sliding property of the object to be washed in a hand-washing lotion, which is to make an organic polymer having a stringiness in the lotion during hand-washing; [3] a method of hand-washing, comprising By the step of washing and washing the cleaned material by hand with a washing liquid, the above washing liquid is a washing liquid containing an organic polymer having a drawing property and indicating a drawing property, or the washing liquid is diluted to more than 1 times with water ~ 1 〇〇〇 times the washing liquid; [4] The method of hand washing and washing according to the above [3], wherein the pH value of the washing liquid is 9.0 99474.doc 200540263 or more; [5] — a detergent composition containing more than 0.1 weight % Of organic polymers having a drawing property of an average molecular weight of 1.5 million or more; [6] The detergent composition according to the above [5], which contains: (a) an average molecular weight of more than 0.1% by weight of 1.5 million or more Stringy organic polymer (B) a surfactant,

(c) Test agent, and (d) Metal ion blocking agent; [7] The detergent composition as described in [5] above, which is powder or granular; [8] As described in [5] to [7] above The detergent composition of any one of the above, further comprising an inorganic salt that emits hydrogen peroxide in water, and the content of the inorganic salt is b% by weight or less; ^ [9] A detergent composition for clothing, which contains an average The molecular weight is "more than 10,000, and 60 mol% or more of the constituting monomer is a polymer having a sulfonic acid group or a salt type group, a sulfuric acid group or a salt type group thereof; π〇] A detergent composition as described above m ' [11] The detergent composition for clothing according to the above [9], comprising: (a,) an average molecular weight of 5 million or more, and 60 mol% or more of the constituent monomers have Polymers having an acid group or a salt group, a sulfate group or a salt group thereof, (b) a surfactant, (c) an alkaline agent, and (d) a metal ion blocking agent; [12] as described above [9 ] To [11], a cleaner composition for clothing 99474.doc 200540263, wherein the constituent monosystem is derived from the group selected from 2-acrylamido-2-methylpropanesulfonic acid and its salts One styrene sulfonic acid and salts of the above monomers; [13] - Species sliding property improving agent which contains an average molecular weight exceeds 〇.1% by weight of 1,500,000 or more and the organic polymer having spinnability;

[14] The slip improver according to the above [13], wherein the organic polymer is a polymer or copolymer, a polysaccharide or a polypeptide having a sugar skeleton, and the polymer or copolymer is derived from a material selected from ethylene oxide, Groups of monomers consisting of acrylic acid, acrylamide, acrylamidine, propanesulfonic acid, dimethylaminoethylamidoacrylic acid, vinyl alcohol, and mixtures of these; [15] —Sliding properties The improver contains a polymer having an average molecular weight of 500,000 or more, and more than 60 mol% of the constituent monomers are polymers having a sulfonic acid group or a salt type group thereof, a sulfuric acid group or a salt type group thereof; [16] as described above [15] The sliding property improving agent, wherein the constituent monomer system is derived from one or more monomers selected from the group consisting of 2 · propenylamine-2-methylpropionic acid and its salt, phenylacetic acid, and its salt Body's base

[17] —A kind of washing method: Those who wash the compound; those who use the cleaning agent set for clothing as described in [9] above. [Embodiment] Focusing on the above aspects, the present invention # y ^ ^. ^ Buzan is about a method for improving the slipping properties of household objects when washing and abandoning them; hand washing 4 "coarse temperature", "forest $ w's 'first / Cui method' which reduces… unpleasant factors or physical fatigue and hand care or washing care; a detergent composition, = use = 99474.doc 200540263 for the above purpose; Moreover, the present invention relates to a cleaning agent composition for clothing materials, which can prevent recontamination by potting, which can reduce the factor called "/ ,,,,,,, and demand; or physical fatigue 'Can also prevent hands: injuries, rubbing: of: fast clothes; a slippery improver; = cleaning agent composition or slippery improver for the clothing of the quilt. Furthermore,' cleaner before the field ' The low molecular weight polymer (such as 1 t sodium propionate or polyethylene glycol) added by the surfactant of the ingredient or the dispersant of mud or carbon, for example, is called a very thick silk (for example, the degree is 100 g / L). In the commonly used washing concentration (for example, as a base concentration ⑽ · G5 g / L ~ 1G0), this effect is not exerted at all, and even when a slight effect is exerted, the above problem of hand washing and washing can not be effectively solved. It is well known For example, the silicide polymer disclosed in the aforementioned Japanese Patent Publication No. Hei 5-508889 has the effect of reducing the friction between fibers, but the user does not know how to wash it with hand washing liquid concentration. I feel a particularly large tactile change. Therefore, by the separate effect of these bases, hand-washing can not achieve a comfortable effect. It is a surface-covering oil agent that reduces the spreadability of fiber surface friction when drying, and prevents water in the aqueous solution. Even with the hand washing using this lotion, the fiber damage caused by hand rubbing will not fully exert the effect. In order to achieve the purpose of comfortable home hand washing and washing, the sliding properties must be achieved with the usual concentration of the lotion. The inventors After re-examining the need to comfortably implement hand-washing, they found the following: By adding specific organic polymers Up to 99474.doc -10- 200540263 hand washing in the lotion, especially when rubbing each other between the objects to be washed, to improve the tactile sensation during hand washing, and at the same time reduce the load on the body, so as to care Clothing and hands. It was found that even in this organic polymer, a polymer having a specific functional group is very excellent in terms of recontamination prevention properties.

In addition, it was found that when the organic polymer is added to a washing solution and washed in a washing machine, the sliding property can prevent clothes from being damaged, and can prevent tangling or deformation in the washing machine due to sliding between clothes or fibers, thereby It has the effect of preventing the care of the clothes. By using the washing method, the detergent composition or the detergent composition for clothes of the present invention, it is possible to exert a more comfortable effect in addition to the usual washing, especially for household hand washing. Specifically, the use of the present invention can improve the tactile sensation at the time of hand washing and alleviate the burden on the body, thereby having the effects of treating clothes and preventing hand abrasions. These and other advantages of the present invention will be made clear by the following description. 1 · Method for improving sliding property The method for improving the sliding property of the object to be cleaned in the washing liquid (hereinafter referred to as "riding property improvement method"), which is more characteristic than A in that: "makes an organic polymer having a stringiness (Referred to as τ, drawing organic matter) exists in the washing liquid.口 妙 u For example, this recipe uses the cleaning residue containing the organic polymer in advance to add solvent water =, or wash the organic polymer that does not contain the stringy organic polymer. . By using a method having related characteristics, the neck can improve the slip of the object to be cleaned. 99474.doc 200540263 Here, "washing liquid" refers to an aqueous liquid composition for washing clothes by dissolving and suspending the detergent composition. In the present invention, "improving the sliding property" means reducing the friction between clothes or fibers in a washing liquid during washing or in a state containing a washing liquid. Especially when washing by hand, the friction is expressed by the degree of resistance that the hand feels when washing the person with the hands.

The sliding property can reduce the resistance (feeling), and it can rub each other's objects smoothly. Specifically, those who perform washing according to the sliding property improving method of the present invention can feel a soft "layer" on the surface when they touch the surface of the object to be cleaned with a fingertip or the like in the washing liquid. It is thought that this is due to the feeling expressed by the stringy organic polymer added to the washing liquid, and this layer or a part thereof exerts an effect as a lubricating layer, so that "smoothness" can be felt in the contacted washing room. In the present invention, since this layer is present in the lotion and "smooth" is generated during hand rubbing, comfortable washing can be achieved. Furthermore, it can also suppress the friction between the object to be cleaned and the hand = cuts, abrasions, etc. (the so-called effect of reducing hand abrasion), and the damage to the fibers and the like of the object to be cleaned (the effect of care of clothes damage) . [Definition of drawability] "Here, drawability refers to the tensile properties of an object, that is, the so-called" drawing, 4 "properties. Examples of notable examples include" natto ". r Stringability, which is caused by dropping the liquid composition at a low speed or holding one end and breaking it when stretched, so that it can express continuous filaments without forming droplets. 99474.doc -12- 200540263 Properties of structures, Examples thereof include "drawing of animal and plant slime" and the like. It is well-known that the following conditions are one of the relaxation characteristics of the liquid composition of the wire-drawing type. The so-called surface tension or viscosity are completely independent physical properties. Here, even with ordinary polymer solutions, as long as the base agent concentration is as high as 100 g / L or higher, the above-mentioned stringability can often be exhibited, but the viscosity of the separated silk is extremely high, and the polymer solution is obvious. Lack of liquidity. The stringability of the present invention refers to the stringiness of a water-based liquid composition of a special organic polymer that can be maintained at a very thin concentration and can exhibit high fluidity. [Definition of stringability of organic polymer] The stringable organic polymer of the present invention refers to an organic polymer whose aqueous solution exhibits the above-mentioned stringability. Generally, the stringable organic polymer is different from a so-called "thickening organic polymer" which is generally expressed as an organic polymer having the same molecular weight. In the present invention, the stringable organic polymer is preferably an organic polymer having a concentration of 300 g / L or less in an aqueous solution, and more preferably an organic solution having a concentration of 10 g / L or less in an aqueous solution. The polymer is particularly preferably an organic polymer in which an aqueous solution having a concentration of 5 g / L or less exhibits stringiness. In the present invention, the presence or absence of stringiness of the organic polymer is determined by the following method. The mixed aqueous solution is prepared, and the stringability of the obtained mixed aqueous solution is determined according to the following [drawability determination method]. When there is a stringiness at any viscosity, it is called a stringable organic polymer. The mixed aqueous solution is based on In an aqueous solution containing 0.07 t / o of sodium undecylbenzoate and 0.07% by weight of anhydrous sodium carbonate, so that the viscosity of the aqueous solution is about 5000 mPa.s, about 200 99474.doc 13 200540263 mPa.s, about 100 mPa.s, about 20 mPa.s (based on B-type viscosity meter, 0. DH, 60 r / min, measured at 25 ° C) polymer concentration added organic polymers. [Drawability determination method] When the dropping operation is performed quietly from a Pasteur straw (glass, such as ASAHITECHNO GLASS, IK-PAS-5P) with an inner diameter of 1 mm at the front end, the drawing aqueous solution is set as the drawing of the present invention. Sexual aqueous solution.

The solution with longer drawing is called an aqueous solution with strong (or high) drawing property. The aqueous solution was thoroughly stirred at 25 ° C for judgment, and the front end of the Pasteur pipette was dropped at least 5 mm from the dropping point. It is easier to confirm the dripping operation of the aqueous solution 'which has a strong drawability. It does not matter if it is confirmed after several dropping operations. Generally, the "silk" 'confirmed during the dropping operation is one having a width smaller than 1 mm. About this physical property, it can also be used by a thermoelectric Hack Co., Ltd. tensile viscosity measuring device CaBER1 (CapiUary such as ~

ExtenSinal Rheometer ‘Capillary tensile rupture rheometer)’ s machine measurement. The higher the effect of wire drawability, the higher the wire drawability of the polymer. When the washing liquid has a wire drawing property 'Although a higher "sliding property" can be achieved, even when the washing liquid does not have a wire drawing property', the washing liquid can contain a polymer having the ability to draw a solution. ". The "sliding usually" purpose of the present invention is the "stretchable organic polymer-based main compound of the present invention. As the stringable organic polymer ^ detergent group, parent-linked polymers and non-99474.doc 200540263 cross-linked polymers are listed. Among them, the non-crosslinked polymer has higher stringability, so it is preferably used in the present invention. Specific examples of the stringable organic polymer include those derived from ethylene oxide, acrylic acid, acrylamide, and 2-propylene. Polymers or copolymers of one or more monomers consisting of amidin-2-methylpropanesulfonic acid, dimethylaminoethylmethacrylic acid, and vinyl alcohol; polysaccharides with a sugar skeleton, which can be listed as powder , Hydroxyethyl cellulose (HEC), carboxymethyl cellulose (CMC), hydroxypropyl methyl cellulose (HPMC), hyaluronic acid; and polypeptides such as polyglutamic acid or polyaspartic acid, etc. Among them, Considering the excellent sliding property improvement effect, acrylic acid polymers or their salts, copolymers of acrylic acid with 2-propenylamine methylpropionic acid or their fluorene, polyethylene polymers, and hydroxypropylmethyl are preferred. Cellulose and hyaluronic acid or a salt thereof. Most of them are crosslinked propylene-based polymers used as thickeners, such as liquid detergents (Akpac, manufactured by Sumitomo Chemical Co., Ltd., and CarbGpol, manufactured by BF Godrich, etc.). The thixotropic nature of 4 can also suppress stringiness, so it can be judged as an organic polymer that does not have stringiness in the present invention. The "14" organic polymer is for the purpose of being added to other detergent ingredients. 'The stringable organic polymer can also be formulated as a slip improver alone or with other compounds. In the case of stringable organic polymerization, one type of polymer can be used, or two or more types of organic polymerization can be used simultaneously ^ It is a slip improver. X, these polymers can also be added to the clean M composition and added. The slip-modifying formula of the present invention > Φ ° & Wash 99474.doc -15- 200540263 = liquid: in terms of quantity, self-improving sliding properties, and

The range is preferably 2 mg / L or more, Yin Quan H. Chinensis 5 mg / L or more, and more preferably 10 balls or more, particularly preferably more than 20 enough, and particularly preferably more than 50 ha. . The period of time when the stringy organic polymer is added to the washing liquid is not particularly limited. Examples thereof include before hand washing and washing, during hand washing and washing, and before immersion when soaking. χ, as the method of adding a stringy organic polymer, a method of directly adding the polymer may be mentioned.

A method of dissolving a solution of ㈣1 such as water is a method in which powders, liquids, gels, etc., in which a material composition is mixed with other compounds are formulated, and the polymer is granulated to add the polymer. The method comprises the method of containing the detergent composition in various forms such as a liquid, a gel, a paste, a powder, a granule, or a tablet, a dough, and the like formed twice. A detergent composition containing a stringy organic polymer may be added to and dissolved in water to obtain a washing liquid, or a stringy organic polymer may be added to an existing washing liquid by the method described above. In any case, the amount of the detergent composition in the washing liquid is not particularly limited. When a detergent composition containing a stringy organic polymer is added and dissolved in water to obtain a washing liquid, the method for producing a detergent composition containing a stringy organic polymer is not particularly limited. It is also known as a method for manufacturing a general detergent composition, for example, Patent Office Publication Nos. 10 (1998) -25 (7159), a well-known conventional technique set (powder cleaner for clothing), or a method disclosed in Japanese Patent No. 3123757. For production, after the detergent components other than the stringy organic polymer can be produced by the above method, the stringy organic polymer is mixed. During mixing, the stringable organic polymer 99474.doc -16- 200540263 can be granulated alone, and mixed with other compounds to form a granulated powder, or even mixed as a liquid or gel-like preparation. In this case, the components other than the stringy organic polymer contained in the detergent composition and the form of the detergent composition are not particularly limited. The sliding property improving method of the present invention does not specifically limit the washing environment, the type of objects to be washed, the amount of objects to be washed, and the amount of the washing liquid. Furthermore, when washing in a container, the size of the container is also not particularly limited. For example, when using a washbasin, 'the larger the washbasin used, the more washing liquid is used, and the lower the bath ratio (the weight ratio of the object to be washed / washing liquid), the easier it is to recognize the sliding property. The size of the washbasin is preferably at least 25 cni in diameter, more preferably at least 30 cm, particularly preferably at least 40 em, and particularly preferably at least 0%. The bath is preferably 1/3 or less, more preferably 1/5 or less, particularly preferably 1/7 or less, and particularly preferably 1/10 or less. Moreover, the solubility of many stringable organic polymers is better at higher temperatures. It is preferably 1 (rc or more, more preferably 20 ° C or more, particularly preferably 25 t: or more, particularly preferably 30 or more. As a hand washing method, as long as it is a hand washing method, The method is not particularly limited. 2 · Hand washing and washing method The present invention relates to a hand washing and washing method. The better hand washing and washing method (hereinafter, referred to as the hand washing and washing method of the present invention) in the present invention includes the following Steps, so that the high sliding property improvement effect can be obtained by practicing the hand washing and washing method: using the sliding property improving method of the present invention, the object to be washed can be washed by hand in the following washing liquid exhibiting stringiness used in the present invention. Therefore, the so-called hand washing and washing effect which can improve the touch feeling and realize comfort can be found. 99474.doc 200540263, and the following effects can also be found: the effect of suppressing hand cuts and abrasions caused by the friction between the object to be cleaned and the hands can be found. (The so-called hand scratch prevention effect), the effect of suppressing damage to the fibers of the object to be washed (the so-called effect of care for the damage of clothes). The so-called hand washing and irrigating method of the present invention It refers to the use of 3 organic polymers with brushability, so that the washing liquid used in hand washing is shown in the drawing or (11) the above washing liquid is diluted to a state of more than 1 to ⑽ times. &Quot; Here, 'the washing liquid which shows the stringiness of the washing liquid is diluted with water exceeding the rigidity of the heart', the washing liquid in the state may not be expressed, but due to the liquid layer between the clothes in the relevant washing liquid There is a stringy organic polymer of the present invention that exhibits lake slippery properties, so the above-mentioned slippery improvement effect of the present invention can be achieved when washing and washing by hand. Therefore, the "aqueous lotion that exhibits stringyness according to the present invention" is an aqueous solution that only thickens. Or the diluted aqueous solution is completely different from the 'in essence. The presence or absence of stringiness of the washing liquid can be determined according to the method of [drawability determination method] described above. The washing liquid exhibiting the relevant stringiness can be determined by the following Ways to obtain: For example, 'drawing organic polymers are used as part of the detergent ingredients or added to the lotion differently from the detergent ingredients. The molecule of this hair towel & The larger the content of the lotion is, the greater the sliding property improvement effect is to achieve a more comfortable wash. The shampoo, which exhibits the stringiness of the present invention, can also be diluted as described above and used in the lotion. 'But considering the improvement effect of sliding property, the concentration when diluted is 99474.doc 200540263

The degree is preferably 1/1 000 or more of the lower limit concentration of the drawing property, more preferably 1/500 or more, even more preferably 1/200 or more, particularly preferably 1/100 or more, and even more preferably 1 / 50 or more, particularly preferably 1/20 or more. In order to further improve the effect of improving the sliding property, it is preferable to use the washing liquid exhibiting the drawing property at a concentration that fully expresses the drawing property. However, considering the operability or economics of the washing liquid, the concentration of the washing liquid is considered. It is preferably 500 times or less, and more preferably 100 times or less, more preferably 50 times or less, more preferably 20 times or less, even more preferably 10 times or less, and more preferably 10 times or less. It is particularly preferably 5 times or less, particularly preferably 2 times or less, and even more preferably 1 time or less. The concentration of the stringy organic polymer in the washing liquid is preferably 2 mg / L or more, more preferably 5 mg / L or more, and more preferably 10 mg / L or more, in terms of obtaining a high sliding improvement effect. , Particularly preferably above 20 mg / L, particularly preferably above 50 mg / L. From the viewpoint of operability as a solution, it is preferably 5,000 mg / L or less, more preferably 2500 mg / L or less, still more preferably 1000 mg / L or less, and particularly preferably 500 mg / L or less. Particularly preferred is 250 mg / L or less. In terms of self-cleanability, the pH value of the washing liquid is preferably 90 or more, more preferably 9 S I ,; I »• 'is particularly preferably 10.0 or more. Here, the pH is 25 ° C and the hardness is 0 in a state of being unclothed. DH measured value. From the viewpoints of stability and prevention of hand chapped skin, the upper limit of the pH value is preferably 11.0 or less. Here, the washing liquid refers to a liquid for dissolving and suspending a detergent composition and the like used to perform washing. In addition, the ingredients other than the organic 99474.doc -19-200540263 included in the detergent composition, the form of the detergent composition, and the manufacturing method thereof are not particularly limited as long as they are used in the above-mentioned method for improving sliding properties. The method is the same. Moreover, in the hand washing and washing method of the present invention, the sliding properties and good methods of the present invention described above are not limited to the hand washing and washing environment, the type of objects to be cleaned, the objects to be cleaned, the amount of water, and the temperature. In the case of washing, the size and the size of the container will also be added, and the washing conditions can be expressed in all environments. Good washing conditions are the same as those described in the above method. Formula 3 · Detergent composition The present invention relates to a detergent composition. The detergent composition of the present invention is classified into the following two aspects. (Aspect 1) A detergent composition containing more than 0.01% by weight of an organic polymer having an average molecular weight of 1.5 million or more and having a drawability. (Aspect 2) A detergent composition for a kind of clothing, which contains an average molecular weight of 500,000 or more and 60 mol% or more of a constituent monomer having a sulfonic acid group or a salt type group thereof, a sulfuric acid group or a salt type group thereof Polymer. (Aspect 1) One of the larger features of the cleaner composition of aspect 1 is that it contains more than 0.1% by weight of an organic polymer having an average molecular weight of 1.5 million or more and having a drawability. The characteristics can thus achieve the following effects: when the detergent composition is used in home hand washing and rinsing, the touch of hand washing can be improved, and at the same time, the burden on the body can be relaxed, and the clothes can also be cared for and hand abrasion can be reduced. 0 99474.doc -20 · 200540263 Also, when washing with a washing machine, it also has the following effects. · Its sliding property can prevent clothes from being damaged, and it can prevent the clothes from intertwining in the washing machine by sliding between clothes, so as to prevent the care of clothes such as swatches. effect. Among them, the detergent composition of aspect 1 preferably contains: (a) more than 0.1 wt. In terms of imparting both detergency and slipperiness. A stringy organic polymer having an average molecular weight of more than 150,000, (b) a surfactant, (c) a test agent, and (d) a metal ion blocking agent. (Aspect 2) The detergent composition of aspect 2 relates to a detergent composition for clothing (hereinafter, referred to as a detergent composition of aspect 2). One of the larger features of the detergent composition of aspect 2 is that it contains an average molecular weight of 500,000 or more and 60 mol% or more of the monomer is a sulfonic acid group or a salt type group, a sulfuric acid group, or a salt thereof. Type polymer (hereinafter referred to as polymer containing sulfonic acid group and / or sulfuric acid group), which has related characteristics, can achieve the following effects: When the detergent composition is used in home hand washing, it can improve The touch of hand washing eases the burden on the body, which can take care of clothes and hands. In addition, when washing with a washing machine, it also has the following effects: its sliding property can prevent clothes from being damaged ', and it can prevent the clothes from intertwining or deforming in the washing machine by sliding between clothes or fibers, thereby preventing care clothes such as aliasing The effect. 99474.doc 200540263 Considering from the two aspects of cleaning composition and slippery property as a cleaner composition of evil sample 2, it is preferred that it contains 60 or more mol% of a monomer, sulfuric acid group, or the like Salt type polymers (a) have an average molecular weight of 500,000 and have a sulfonic acid group or a salt type group thereof (b) a surfactant, (c) a test agent, and (d) a metal ion blocking agent.

Ten, one of my dosage forms, such as powder, granules, liquid or paste, is also formed into aggregates, tablets, and tablets. In terms of self-cleaning, there are surfactants and alkaline agents or metal ion blocking agents. From the viewpoint of the solubility of the detergent composition, it is preferred to disperse the base quickly when dissolved. From these viewpoints, 'is preferably powdery or granular. In addition, the invention is a stringable organic polymer or a polymer containing money-based and / or sulfuric acid groups, which are basically powders or granules, and can be easily formulated because the detergent composition is powdery or granular. And the polymer has a greater degree of freedom. -The manufacturing method of the detergent composition of the present invention is not particularly limited. It can be manufactured according to a method known as a method for producing a general detergent composition, for example, the Patent Office Publication 10 (1998) -25 (7159), a well-known conventional technology set (powder cleaner for clothing), or a method disclosed in Japanese Patent No. 3123757. After the above-mentioned method is used to produce a stringable organic polymer or a detergent component other than a polymer containing a sulfonic acid group and / or a sulfuric acid group, the stringable organic polymer or a polymer containing a continuous acid group and / or a sulfuric acid group is mixed. 99474.doc -22- 200540263 Furthermore, the detergent composition of the present invention as shown in aspect 1 or 2 can be preferably used for the above-mentioned method for improving the sliding property of the present invention or the hand-washing method of the present invention. The detergent composition of the present invention, which is different from the aspect 1 or 2, can be used as a general hand washing detergent or a washing machine when used in the case of the sliding improvement method of the present invention and the hand washing method of the present invention. Use in general usage and concentration. As the concentration of the detergent composition in the washing liquid, in the case of hand washing and washing, from the viewpoint of improving the sliding properties of the washing liquid, it is preferably 0.05 g / L or more, more preferably 0 g / L or more, Furthermore, it is more preferably 0.5 g / L or more, particularly preferably lg / L or more, even more preferably 2 g / L or more, and particularly preferably 3 g / L or more. On the other hand, from the viewpoint of self-cleaning property or operability of the washing liquid, it is preferably 20 g / L or less, more preferably 15 g / L or less, and particularly preferably 10 g / L or less. It is particularly preferably used at a concentration of g / L to 10 g / L. In addition, as a preferred method of use, the following method can be mentioned: a proper amount of the cleaning agent composition of the present invention is sprinkled on a hand-washed part of the "clean clothes" part, and it is brought into contact with water to make washing Liquid and hand wash. It is preferably used in combination with a detergent composition other than the detergent composition of the present invention, or in combination with a composition for clothes care which does not contain a cleaning ingredient such as a perfume composition. Hereinafter, each component used in the present invention will be described. • 4. Stringable organic polymers and polymers containing acetic acid groups and / or sulfuric acid groups are used in the detergent composition of the present invention, by using the stringable organic polymers described in the method for improving sliding properties of the present invention Therefore, the sliding improvement effect of the present invention can be obtained, but it is preferable to use flat 99474.doc -23- 200540263 as the stringable organic polymer. The larger the water-soluble organic having an average molecular weight of 1.5 million or more, the smaller the amount of organic polymerization. Materialization; second nature. " As long as the average molecular weight is -10,000 or more, the stringability is two: even in low substrate concentration like washing liquid, ^ °, J fully imparts sliding, even in thinner concentration, it can fully realize "sliding ν? ± mobility" consideration The average molecular weight is preferably more than 2 million, more preferably 250,000 tombs from above, and particularly preferably more than 3 million. m, from the viewpoint of solubility, average molecular weight

It is preferably below 10 million, more preferably below 30 million, and particularly preferably below 20 million. The polymer containing a sulfonic acid group and / or a sulfuric acid group according to the present invention may be a vinyl polymer ' material, a polycondensation polymer, or a polyether polymer. When the polymer containing a sulfonic acid group and / or a sulfuric acid group of the present invention is a vinyl-based polymer, the monomer unit has a sulfonic acid group and / or a salt-type group thereof, and / or a sulfuric acid group and / or Examples of the vinyl-based constituent monomers of the salt-type group include 2- (meth) acryloxyethyl benzene acetic acid, 2- (meth) propanyl oxypropyl carboxylic acid, and 2- ( (Methyl) Acrylic acid-2-carbonyl (carbon number 1 to 4) acrylic acid, ethylidene acid, allyl lutein acid, styrene acid, vinyl sulfuric acid, etc. . Among them, since it is easy to obtain a polymerizable high molecular weight body, it is preferably derived from 2- (fluorenyl) propenyloxyethanesulfonic acid, 2- (meth) propenyloxypropanesulfonic acid, 2- (Meth) acrylamine-2-yl (carbon number 1 ~ 4) propane and phenyl ethyl acid, etc. are more preferably derived from 2-acrylamido-2-methyl The groups of propanesulfonic acid and styrenesulfonic acid are particularly preferably those derived from 2-propenylamine-2-fluorenylpropanesulfonic acid. 99474.doc -24- 200540263 These constituting monomers can also be used in the acid form, or they can be used as a salt form by neutralizing some or all of the sulfonic acid group and / or sulfate group with a base. -As a counter ion forming a salt type group of a sulfonic acid group or a sulfuric acid group, a metal ion, an ammonium ion, an alkyl or alkenyl ammonium ion having a total carbon number of 1 to 22, and an alkyl group having a carbon number of 1 to 22 may be mentioned Or alkenyl-substituted pyridinium ions, and alcohol ions having a total carbon number of 22, preferably metal ions such as sodium ions and potassium ions, or ammonium ions, and sodium ions and potassium ions are particularly preferred. In the polymer containing a sulfonic acid group and / or a sulfuric acid group of the present invention, the above-mentioned constituent monosystem may be used alone or in combination of two or more kinds. When the constituent monomers are two or more, the constituent monomers are used as the constituent monomers. The configuration of the body is not particularly limited, and may be randomly arranged, alternately arranged, or block-arranged. In the case of a polymer-based ethylene-based polymer containing a confirmed modified group and / or a sulfuric acid group in the present invention, the method for synthesizing the ethylene-based polymer is not added, particularly limited, and a well-known one can be selected. method. For example, it is possible to separately polymerize ethylenic monomers containing acid groups (and / or their salt-type groups), amidine, and / or sulfate groups (and / or their salt-type groups). The mole fraction of the monomers and other early forms that do not contain a continuous acid group (and / or its salt type group) and / or a sulfate group (and / or its salt type group) is 60 mole%. The above ratios are copolymerized ^. Or, it may constitute a ratio of 60 mol% or more of the monomer, and the K group (and / or its salt type group) and / or the sulfate group (and / or its salt type group) may be introduced into the existing After using any polymer. : In the case of a polymer-based vinyl-based CT containing a sulfonic acid group and / or a sulfuric acid group according to the present invention, the sulfonic acid group containing 99474.doc -25- 200540263 (and / or Salt-based group) and / or sulfate-based (and / or its salt-based) monomers are a method and polymerization method for obtaining a vinyl polymer, although they can be used for overall polymerization or sink polymerization. Higher polymers can also be synthesized by aqueous polymerization or reverse-phase suspension polymerization, taking into account the ease of polymerization control.

In the case of a polymer-based vinyl-based polymer containing a sulfonic acid group and / or a sulfuric acid group of the present invention, a polymerization method for synthesizing an acetamyl-based polymer may also be a radical polymerization, an anionic polymerization, or a cationic polymerization. And polycondensation, when synthesizing a vinyl polymer by radical polymerization, potassium persulfate, ammonium persulfate, sodium persulfate, t-butyl hydrogen peroxide, and Peroxide-based initiators such as hydrogen peroxide ^ Azo-based initiators such as 2,2'-azobis (2-fluorenylpropane) dihydrochloride can also be used. Agent and sodium sulfite, sodium bisulfite, ferrous sulfate, L-ascorbic acid and other reducing agents and used as a redox-type initiator after use, can also be irradiated with ultraviolet rays, electron rays, gamma rays, etc., and start polymerization. Furthermore, 'for the use amount of the polymerization initiators of the above-mentioned vinyl-based monomers, it is preferably 0.0001 to 5 mol%, more preferably 0.001 to 15 mol / 〇', and particularly preferably 〇. 〇1 ~ 0.5 Molar%. In the case of synthesis of an ethynyl polymer by anionic polymerization, an aromatic complex of an alkali metal such as naphthyl sodium or an alkali metal such as bell, sodium, or potassium, η-butane can be used as the polymerization initiator. Organolithium compounds (alkyl lithium compounds) such as lithium, t · butyllithium, methyllithium, or fluorenyl bell, and organomagnesium & compounds', preferably phenylmagnesium bromide or butyl bromide Grignard compounds such as magnesium sulfide 'or diorgano 99474.doc -26- 200540263 magnesium compounds such as dibenzyl magnesium, dibutyl magnesium, or benzyl pyridyl magnesium. Furthermore, the amount of the polymerization initiators used for the above-mentioned vinyl-based monomers is preferably 0.0001 to 5 mole%, more preferably 0.001 to 15 mole%, and particularly preferably 0.01 to 0.5 mole 0 / 〇.

On the other hand, when a vinyl polymer is synthesized by cationic polymerization, as the polymerization initiator, Bronst such as trifluoroacetic acid, trigas acetic acid, sulfuric acid, methyl acetic acid, and trifluoromethane acid Acid, water / boron trifluoride, water / boron trigas, water / aluminum vapor, water / aluminum bromide, water / tin tetragas, triacetic acid / tin tetragas, hydrogen gas / Bronsted boron or hydrogenated gas / Sanluanhuashao and other Bronsted acid / Lewis acid mixtures, and organic cations such as triphenylsulfonium cations, rust cations, etc., or gasified acetamidine / hexafluoroantimony Mixtures of oxygen-containing carbon rust ions such as silver acid or vaporized acetamidine / peroxy acid silver. Furthermore, the amount of the polymerization initiators used for the above-mentioned vinyl-based monomers is preferably 0.0001 to 5 mole%, more preferably 0.001 to 1.5 mole 0/0, and particularly preferably 0.01. ~ 0.5 mole%. Also as a copolymer of other monomers that can be copolymerized with a monomer having a sulfonic acid group (and / or its salt-type group) and / or a sulfuric acid group (and / or its salt-type group) to obtain a vinyl system In the case of a polymer, a constituent monomer other than a constituent monomer having a sulfonic acid group (and / or its salt-type group) and / or a sulfate group (and / or its salt-type group), as long as it contains a sulfonic acid group and / Or the sulfuric acid-based polymer can maintain water solubility, that is, it is not particularly limited. Examples of such a copolymerizable monomer include the following. It is (meth) acrylic acid [(meth) acrylic acid refers to acrylic acid, methacrylic acid or a mixture thereof] and its salts, styrene carboxylic acid and its salts, maleic acid-based monomer [maleic anhydride , Maleic acid, maleic acid monoester, and maleic acid 99474.doc -27- 200540263 monoamine or a mixture containing two or more of these] and its salts, itaconic acid and its salts, etc., can be It is selected from the following: m), which is easy to copolymerize, so (meth) acrylic acid and its salts, styrene acid and its salts, and more preferably methyl) acetic acid and Its salts. Here, as the counter ion forming the salt, the above counter ion may be used.

Further, a vinyl-based constituent monomer having a phosphate group (or a salt type group) or a phosphonic acid group (or a salt type group) thereof may be copolymerized. For example, (meth) acrylic fluorenyloxyalkyl (carbon number 1-4) phosphoric acid, vinylphosphonic acid, etc. are mentioned. Here, as the counter ion forming a salt, the above counter ion may be used. Furthermore, the following monomers may be copolymerized. 1) Substitute unsubstituted (meth) acrylamide or (meth) acrylamide with nitrogen atom substituted with saturated or unsaturated alkyl or aralkyl group with carbon number of ～ 4 class. For example, (meth) acrylamide, N-methyl (meth) acrylamide, N, N-dimethyl (meth) acrylamide, ethyl (meth) acrylamide, Nt-butyl (meth) acrylamide, (meth) acrylfluorenylmorpholine, 2_ (N, N-diamidinoamino) ethyl (meth) acrylamide, 3_ (N, N • Dimethylamino) propyl (meth) acrylamide, 2-hydroxyethyl (meth) acrylamide, N-hydroxymethyl (fluorenyl) acrylamide, and N-butoxymethyl ( (Meth) acrylamide. 2) (meth) acrylates. For example, methyl (meth) acrylate, ethyl (meth) acrylate, 2-hydroxyethyl (meth) acrylate, and 2- (N, N-diamidoamino) (meth) acrylate are preferred. Ethyl ester, 2-methoxyethyl (meth) acrylate, and polyethylene glycol (fluorenyl) acrylate. In addition, the polymer containing a sulfonic acid group and / or a sulfuric acid group of the present invention may also be 99474.doc -28-200540263 ..., and the degree of palatal linkage is preferably not a degree of gelation. That is, for the crosslinking amount used at the time of Polymer 3, it is preferably 0 to 0.001 mol 0/0 in the constituent monomers.

Examples of the parent cross-linking agent include ethylene glycol di (meth) acrylate, diethylene glycol mono (meth) acrylate, polyethylene glycol di (meth) acrylate, and glycerol mono (meth) Acrylate, dipropylene glycol di (meth) acrylate, polypropylene glycol mono (meth) acrylate, 1,2-butanediol di (meth) acrylate 酉 θ 1'3-butanediol di (methyl) ) Acrylic esters, neopentyl glycol di (meth) acrylic slogans, propylene glycol di (meth) acrylates, glycerol tri (meth) acrylic acid 酉 ——- via methyl propylene tris (meth) (Meth) acrylate compounds of polyhydric alcohols such as acrylate and pentaerythritol tetra (meth) acrylate; small methallyl allylamine, N-vinyl allylamine, N, Nl methylidene bis (methyl) ) Acrylamine compounds such as acrylamine and bisacrylamine acetic acid; divinylbenzene, divinyl ether, and divinylethylene urea, etc. Dipropyl acrylate, dipropylamine, triallylamine, triallylammonium salt, Allyl etherified body of pentaerythritol and polypropylated compound of dilute propyl etherified body 4 of sucrose having at least two dilute propyl ether units in the molecule; ethylene (meth) acrylic acid ester , Unsaturated (meth) acrylates of unsaturated alcohols such as propyl (meth) acrylate and 2-hydroxy-3-propenyloxypropyl (fluorenyl) acrylate. Among these crosslinking agents, ethylene glycol di (meth) acrylate, polyethylene glycol di (meth) acrylate, divinylbenzene, pentaerythritol triallyl ether, and pentaerythritol tetramethylpropyl are preferred. key. In addition to the copolymerization with the above-mentioned crosslinkable polymer, it is also possible to use 99474.doc -29- 200540263 to use 1,2-ring 4 > in butane, 丨, 2 · epoxyhexane , 1,2_epoxy octane, and 丨, 2 · ring #, ... The reaction of the oxygen compound of the nettle is used for cross-linking, and the following cross-linking method can also be used. · Self-crosslinking and polymerization during polymerization Cross-linking reaction between objects, radiation irradiation and other methods of covalent bond cross-linking, via metal ion and other parent links, hydrogen-bonding cross-linking, cross-linking from partial crystalline structure and spiral structure Of cross-linking and so on.

In the case where the polymer containing a sulfonic acid group and / or a sulfuric acid group of the present invention is a non-rare earth-based compound, it may also be a polymer, polyamine, polyurethane, and polyimide. The polycondensation polymer may be a polyether polymer. Or, in any existing polycondensation polymer or polyether polymer, a sulfonic acid group (and / or its salt type group) may be introduced at a ratio of 60 mol% or more of the constituent monomers, Use after sulfate group (and / or its salt type group). In the case of polymers containing sulfonic acid groups and / or sulfuric acid groups, when considering the need to use the representative dirt particles of the cleaning agent, that is, solid particles of mud or coal ash, the affinity of the washing liquid with these arbitrary dirt particles is considered Lower. Therefore, even when arbitrary particles such as mud and coal ash are present in the washing bath, when the high polymer of the polymer is present in the washing solution at a concentration that can exhibit the sliding property, it is simultaneously adsorbed to a plurality of particles so as not to Causes agglutination, so it becomes a binder between fibers and particles, making it difficult for dirt to adhere to clothes. That is, in the case where the stringable organic polymer of the present invention is a polymer containing a sulfonic acid group and / or a sulfuric acid group, among the monomers constituting the polymer, these acid-based monomers and sulfuric acid-based monomers are moles. The more fractions, the better. A constituent monomer containing a sulfonic acid group (and / or its salt-type group) or a sulfate group (and / or its salt-type group):） 'It is preferably 60 mol% to 99474 of all the constituent monomers. .doc • 30 · 200540263, more preferably 66 mol% or more, particularly preferably 85 mol% or more, particularly preferably 95 mol% or more. As the polymer containing a sulfonic acid group and / or a sulfuric acid group of the present invention, a molecule with a time-average molecular weight of 5 million or more can be used. The larger the average molecular weight, the smaller the "sliding property" can be achieved. As long as the polymer has an average molecular weight of 500,000 or more, the slip property can be sufficiently imparted to clothes. Considering that the sliding property can be fully achieved even at a thinner concentration, the average molecular weight is preferably at least 1 million, further preferably at least 1.5 million, more preferably at least 2 million, and even more preferably at least 2.5 million. Particularly preferred is 3 million or more, and further particularly preferred is 4.5 million or more, particularly preferred is 5 million or more, particularly preferred is 6 million or more. However, considering the solubility, the average molecular weight is preferably 30 million or less, more preferably 20 million or less. In addition, among the physical properties of the polymer containing a sulfonic acid group and / or a sulfuric acid group of the present invention, a physical property that exhibits a good "sliding property" is "drawing property". The higher the drawability of the polymer, the smaller the amount of addition can be to show "sliding". In the present invention, the so-called higher stringability refers to the case where lower concentration aqueous solution and lower viscosity aqueous solution exhibit stringiness. 越高 The higher the molecular weight, the lower the crosslinkability of a linear polymer, the stringability. The higher the value, the better the "sliding property" is and therefore the better polymer of the present invention. [Definition of average molecular weight] The average molecular weight of the organic polymer used in the present invention can be determined by gel, permeation, and chromatography (GPC) measurement under the following measurement conditions. Polyethylene oxide (PEO) was used as the standard sample, and the molecular weight was calculated using pE0. In addition, in the present invention, the number average molecular weight or weight average molecular 99474.doc • 31-200540263 amount is not used, but the PEO conversion value (hereinafter referred to as the peak top molecular weight) of the highest dissolution fraction detected by the GPC dissolution curve is used. ) And set it as the average molecular weight. That is, for example, the "organic polymer having an average molecular weight of 1.5 million or more" refers to an organic polymer having a peak top molecular weight of 1.5 million or more in terms of molecular weight in terms of PEO. [GPC method measurement conditions]

For the column system, PW / GMPWXL / GMPWXL (manufactured by Tosoh Co., Ltd.) was used, and 0.2 M phosphate buffer (KH2P〇4, Na2HP04, pH = 7) / CH3CN = 9 / l (weight ratio) was used in the eluent. Column temperature: 40 ° C, flow rate: 1.0 mL / min, sample concentration is 1 ~ 100 gg / mL. The detector used RALLS (90Q light scattering analyzer). When the constituent monomer contains a sulfonic acid group or a salt type group thereof, a sulfuric acid group or a salt type group thereof, an approximate value of the average molecular weight can be estimated using a RID (differential refractometer). GPC analysis using RID can be determined, for example, as a column: GMP WXL + GMP WXL, eluent: 0.2 M phosphate buffer / CH3CN = 9/1 (weight ratio), column temperature: 40 ° C, flow rate: 0.5 mL / min, concentration: 0.05 mg / mL. Furthermore, RALLS can be used as a detector. The present invention relates to a modifier (hereinafter, referred to as the slip improver of the present invention), and the modifier is a polymer obtained by polymerizing the stringable organic polymer or containing a sulfonic acid group and / or a sulfuric acid group. The object exhibiting the sliding improvement effect of the present invention. The form of the slip improver of the present invention is not particularly limited, and it can be any dosage form such as powder, granule, liquid, or slurry / paste form, or it can be formed into an aggregate by secondary processing. , Granules and tablets 99474.doc -32- 200540263 and so on. As such a molding method, a well-known method can be used. The sliding property improving agent of the present invention can significantly increase its lubricity by adding / dissolving in water or other water-based composition. Therefore, the slip improver of the present invention can be improved to the above-mentioned cleanser composition of the present invention by adding it to a general cleaner composition.

'= The fact that the slippery improver of the present invention is added to a general detergent composition to obtain the cleansing composition of the present invention is not particularly limited as a method for adding the slippery improver of the present invention', but is a sufficient expression As the effect of improving the sliding property, the following addition method is preferred: In the manufacturing step of the detergent composition, the sliding property improving agent of the present invention is uniformly dispersed in the cleaning agent composition. Normally, in the powder detergent manufacturing process, it can also be blended later (add detergent ingredients to the prepared detergent particles, such as fluorescent dyes, perfumes, defoamers, whiteners, and bleaching activity Step of chemical agent, etc.) Adding the sliding property improving agent of the present invention may also be added during the surface modification step and the granulation step. If possible, it can also be added in the slurry mixing step. In the case of a polymer powder or granule containing a sulfonic acid group and / or a sulfuric acid group, it is preferable because it can be directly mixed with a powder or granular detergent composition. Although the physical properties of the polymer particles are not particularly limited, in consideration of the solubility of the polymer particles, the average particle diameter is preferably 3 · or less, more preferably 以下 1 mm or less', and particularly preferably _ ton or less. From the point of view of the cleaning agent, and the dispersibility of σ-physical agent in water, and the prevention of agglomeration, the average particle diameter is preferably 10 Å or more, more preferably 50 μm or more, and particularly preferably 10 G μm or more. The method for producing a polymer containing a continuous acid group and / or a sulfuric acid group 99474.doc -33-200540263 is not particularly limited, but in consideration of obtaining a powder or a granular polymer having the above-mentioned particle size, it is preferable to reverse it. Phase suspension polymerization. It is also a stringy organic polymer or a polymer containing sulfonic acid group and / or sulfuric acid group, which inhibits agglomeration (due to the hydration of a part of the particle agglomerates, etc., particle adhesion occurs and will not disperse even if mechanical force is applied It can be used as a mixture of granulation and other bases. The other bases described herein may be any bases that can sufficiently disperse / dissolve the stringable organic polymer or the polymer containing a sulfonic acid group and / or a sulfuric acid group of the present invention. Use awnstone, sodium carbonate, zeolite, polyethylene glycol, or pyrosulfate. The content of the stringy organic polymer or the polymer containing a continuous acid group and / or a sulfuric acid group in the detergent composition is preferably more than 0.1% by weight from the viewpoint of improving the hand-washing property (for example, sliding property). The amount is more preferably 0.3% by weight or more, particularly preferably 0.5% by weight or more, and even more preferably 1% by weight. The above is particularly preferably 3% by weight or more. In consideration of detergent properties and powder physical properties, the weight is preferably 30% by weight or less, more preferably by weight% or less, and particularly preferably ≦ 0% by weight /%. In addition, in hand washing and washing, there is a case where the washing is performed under a small amount of washed objects or water. Therefore, compared with the case of washing the washing machine, the detergent composition is mostly used in a smaller amount each time. In particular, a powdered detergent composition obtained by blending a powdery organic polymer content or a polymer content containing a sulfonic acid group and / or a sulfuric acid group with powder detergent particles is considered to be uniform. Blended with a brushable organic polymer or a polysulfonic acid group and / or sulfate group-containing polymer contained in each use of the detergent composition 99474.doc -34-200540263 Composition φ, all together! The content of the organic polymer or the polymer containing a sulfonic acid group and / or a sulfuric acid group is preferably more than 0.1% by weight, more preferably 0.2% by weight / 0 or more, and even more preferably 03% by weight. ❶ / ❶ or more, particularly preferably 0.5% by weight or more, and even more preferably Q 7% by weight or more, and particularly preferably b weight. / 〇 or more. In consideration of the mixing balance, it is preferably 20% by weight or less, more preferably 10% by weight or less, and still more preferably 5% by weight or less.

In the case of using the stringable organic polymer of the present invention, in consideration of stabilization of the amount of use of the stringable organic polymer, in the case of mixing with other components in the form of granulation or the like, it is possible to reduce the amount of The active ingredient thus has good dispersibility of the polymer in the composition and is therefore preferred. 5. Other detergent ingredients <(b) Surfactant> As the surfactant used in the present invention, previously known substances can be used. Furthermore, in view of improving the cleaning property, it is preferable to use an anionic surfactant and a nonionic surfactant as the main surfactant as the surfactant. In particular, as the anionic surfactant, it is preferable to have a carbon number of 18. Straight-based benzoic acid salts, thiosulfonic acid esters, polyoxyalkylene alkyl ether sulfates, α-sulfo fatty acid methyl ester salts, sorbyl amino acid-based surfactants, alkyl groups Or alkenyl ether carboxylates, amino acid-based surfactants, alkenyl or alkenyl salts or salts thereof, and fatty acid salts derived from tallow or palm oil can also be added. Alkylbenzenesulfonic acid 99474.doc -35 · 200540263 salt, alkyl sulfate ester salt, polyoxyalkylene alkyl ether sulfate, and particularly preferred is sodium alkylbenzenesulfonate. The anionic surfactant has the effect of further improving the "drawability" of the organic polymer specified in the present invention, or increasing the "sliding property imparting effect" of the organic polymer. Considering this aspect, the content of the anionic surfactant in the detergent composition is preferably 5% by weight or more, more preferably ο% by weight or more, even more preferably 12% by weight or more, and particularly preferably 15% by weight. ❶ / ❶ or more, more preferably 18% by weight or more, particularly preferably 20% by weight or more. Considering the physical properties of the powder, it is preferably 40% by weight or less, more preferably 35% by weight or less, particularly preferably 30% by weight or less, and particularly preferably 26% by weight or less. The nonionic surfactant is preferably a polyoxyalkylene [preferably ethylene oxide and / or propylene oxide] alkyl ether. Polyoxyethylene alkyl phenyl ethers' higher fatty acid alkanolamines or their alkylene oxide additions, sucrose fatty acid esters, alkyl glycosides, and fatty acid monoglycerides can also be used. Non-ionic surfactant, which has good hard water resistance and excellent cleaning power to remove oily dirt such as sebum dirt. In view of foaming properties and washing properties, it is preferred to use M% by weight or less. Furthermore, surfactants such as betaine-type amphoteric surfactants, phosphate ester-based surfactants, petrolatum, and cationic surfactants can be suitably added to the detergent composition of the present invention. &lt; (c) Alkali agent &gt; As a test agent used in the present invention, it is good to add a previously known alkali agent. In consideration of detergency, it is preferable to add an alkaline agent to the detergent composition. Examples of tinctures include alkali metal carbonates such as dense ash or sparse 99474.doc -36- 200540263 pine ash, sodium carbonate, and amorphous metals such as JIS No. 1, No. 2, and No. 3 sodium silicate. Alkali metal silicate, crystalline alkali metal silicate, etc. The alkali metal salt has the effect of further improving the "sliding property" of the organic polymer specified in the present invention. Considering this aspect, the content of the alkali metal salt in the detergent composition is preferably 丨 wt% or more, further preferably 5% by weight ❶ / ❶ or more, more preferably 7% by weight or more, and even more preferably 丨^ Weight% or more 'is particularly good! More than 2% by weight, and further particularly preferably, again. The above is particularly preferably 20% by weight or more. In consideration of the mixing ® balance, it is preferably 40% by weight or less, and more preferably 30% by weight or less. &lt; (d) Metal ion blocking agent &gt; A metal blocking agent is added to the detergent composition as a synergist, and considering the detergency, the effect of catching the hardness components in the washing water is very good. Moreover, the metal ion blocking agent 'has the effect of further improving the "sliding property" of the polymer specified in the present invention. In particular, the effect of adding a metal ion blocking agent with a calcium ion capturing energy of 100 mg CaCOVg or more is particularly good. Examples of related% metal ion blocking agents include crystalline aluminosilicates, crystalline sodium silicates, acrylic polymers, acrylic acid-maleic acid copolymers, sodium tripolyphosphate, ethylenediaminetetraacetic acid, and methylglycine diacetate. acetic acid. However, the metal ion blocking agent in the present invention does not contain sodium carbonate or amorphous sodium silicate. Considering the detergency, the content of the metal ion blocking agent in the detergent composition is 3 :, k is preferably 1% by weight or more, more preferably 5% by weight or more, particularly preferably 10% by weight or more, and particularly preferably It is 20% by weight or more. Considering the aspect of mixing balance, it is preferably 50% by weight or less, more preferably 40% by weight / 0% or less, particularly preferably 35% by weight or less. 99474.doc -37- 200540263 &lt; (e) Inorganic salt emitting hydrogen peroxide &gt; In addition, considering the so-called "reduction of skin irritation on the hands", it is preferable to release hydrogen peroxide in water as a cleansing composition. If the content of the inorganic salt (hereinafter referred to as a hydrogen peroxide emitting substance) is less than 15% by weight, more preferably less than 10% by weight, particularly preferably less than 5% by weight, particularly preferably less than 2.5 weight. / 〇.

The hydrogen peroxide emitting body is not particularly limited, and examples thereof include percarbonate, perborate, perphosphate, and persilicate. &lt; (f) Other polymers &gt; Also used in the detergent composition of the present invention or in the cleaning solution of the present invention, in addition to the organic polymer having a drawability, it can also be added to improve the solid particle dirt. Previously known organic polymers with a molecular weight of less than 500,000 for the purpose of dispersibility, etc., preferably organic polymers with a molecular weight of 10 to 100,000, such as carboxylic polymers, polyethylene glycols, and carboxymethyl cellulose Wait. &lt; Carboxylic acid polymer &gt; In addition to the function of blocking metal ions, the carboxylic acid polymer has a function of dispersing solid particle dirt in a washing bath. The carboxylic acid polymer is a homopolymer or copolymer of acrylic acid, methacrylic acid, itaconic acid, and the like. The copolymer is preferably a copolymer of the above monomer and maleic acid, and the molecular weight is preferably 5,000 to 20,000 people. &lt; Polyethylene glycol &gt; Polyethylene glycol has a function of dispersing solid particle dirt in a washing bath. The branch is preferably one with a molecular weight of 1,000 to 20,000. 99474.doc -38- 200540263 &lt; Carboxymethylcellulose &gt; The retarded methylcellulose system has a function of dispersing solid particle dirt in a washing bath. In view of dispersibility, those having a molecular weight of several thousands to several hundred thousand and a test degree of 0.2 to 1.0 are preferred. &lt; (g) Other additives &gt; To the detergent composition of the present invention, enzymes, perfume dyes, pigments, and the like may be added. 6 · Washing method

The invention relates to a washing method. The washing and filling method of the present invention is characterized by comprising the steps of using the cleaning agent composition of the present invention, adding the stringy organic polymer of the present invention or a cleaning agent composition containing a Wei group and / or a sulfuric acid group-containing polymer. Or, the detergent composition of the present invention that adds the sliding property improving agent to wash the object to be washed, and because it has related characteristics, it can obtain the sliding property between the objects to be washed, and exhibit fibers that inhibit the object to be cleaned. And other damage effects (the so-called care effect of clothes damage). In the case of hand-washing, the effect of so-called hand-washing can be improved by improving the touch. Furthermore, it is possible to exhibit the effects of suppressing hand cuts and abrasions caused by friction between the object to be cleaned and the hands (the so-called effect of reducing hand abrasions), thereby achieving the sliding improvement effect of the present invention. The larger the molecular weight of the wire-drawing organic polymer or the polymer containing sulfonic acid group and / or sulfuric acid group, the larger the content in the washing liquid, the more the sliding property can be improved, and the washing liquid can also be improved. The drawability makes it possible to achieve more comfortable washing. The washing liquid in the washing method of the present invention may be the same as that shown above 99474.doc -39- 200540263. Also, in the washing method of the present invention, The washing environment, the type of washed objects, the amount of washed objects, and the amount of water are not particularly limited, and when the container is washed in the middle, the size of the container is not particularly limited, and it can be displayed in all environments. Effect In the following, the embodiment of the present invention will be further disclosed and described by way of the embodiment. This embodiment is merely an illustration of the present invention and does not have any limited meaning. Measurement of molecular weight) The molecular weight of each organic polymer used in this example was measured by the method described above. A RALLS was used as a detector. Sample 1 Sodium polyacrylate (ArOn A-20 P) manufactured by East Asia Synthesis Co., Ltd. Sample 2 Acrylamine methylpropane sulfonic acid / acrylic acid copolymer-Na (Aron A-50 P) manufactured by Toa Kosei Co., Ltd. Sample 3 Polyethylene oxide (pE〇8z) manufactured by Sumitomo Refining Co., Ltd.% Sample 4 Sumitomo Refined (manufactured) polyethylene oxide (PE03) measurement results Sample 1 (peak) average molecular weight 5 million samples 2 (peak) average molecular weight 5.5 million samples 3 (peak) average molecular weight 2.8 million • sample 4 (Peak value) The average molecular weight is 1.2 million, and the hand-washing and washing evaluation methods performed in the examples are shown below. &Lt; Hand-washing and washing evaluation methods &gt; ° [Hand-washing and washing conditions] 99474.doc 200540263 will be adjusted to 25 ° C and equivalent 8.9 mg of CaC03 / L in 2 L of hard water (Ca / Mg molar ratio is 7/3) was filled in a polypropylene washbasin (manufactured by Yazaki) with a diameter of 30 cm, a depth of 13 cm, and a capacity of 8.2 L. After putting 15 g of the detergent composition into water Water will not stir from his hand would continue its degree of scattering washbasin

mix. Thirty seconds after the start of the immersion, the 100% cotton T-shirt (white L made by Gunze) was soaked in the lotion in the washbasin by completely soaking the entire T-shirt. After five minutes, hold the T-shirt chest with both hands And rub each other between the chest of τ shirt. at this time

The parts rubbing each other are washed in a state of being taken out of the lotion. After kneading two to five times each time, immerse the kneaded part in the lotion. The ease of rubbing during rubbing was judged to be slippery, and it was divided into 5 grades. When using only the adjustment of water as described above, the folds of the T-shirt will hinder the sliding property, and because there is no foam in the kneading points, it is very difficult to knead and the sliding property is poor. Set this time to sliding: 丨. The status of each level is shown below. Rank 1 · Sliding property is very low, there is friction, and it is very difficult to wash by hand. Level 2 · Low mobility and friction, making it difficult to wash by hand. Etc., and 3 · The sliding property is medium and non-friction, and can be washed by hand. Level 4/4 is relatively mobile, with no friction and easy to wash by hand. Level 5: Very high sliding property. No friction, easy to wash and fill by hand. Furthermore, in the above-mentioned test, the average value of the evaluation results obtained by the six professionals was set as a grade. Also, "about the stringiness of the lotion obtained by the above-mentioned hand-washing and washing method evaluation method" was measured by dissolving 15 g of a cleansing age compound in an 86 ... water towel "stringability determination method". (&Lt; Cloth damage test &gt; 99474.doc • 41- 200540263 (Preparation of pre-treatment cloth) Set the washing water volume of automatic washing machine (Toshiba, AW-D802VP) to 45 L, put 10 pieces of cotton here T-shirt (approximately 2.2 kg). In addition, according to the standard usage, put in powder type powder cleaner (attack, Kao (strain)), wash for 8 minutes, dehydrate for 3 minutes, rinse twice, and dehydrate for 3 minutes, then use a dryer Dry. Repeat this washing cycle five times, and set it as a pre-treatment cloth. (Cloth damage test)

In the above-prepared T-shirt, Shimaki's chest was stitched with a sewing machine using Testfabrics, MA (Machine Action) test cloth manufactured by Inc. The MA test cloth is based on Frants Szaras; &quot; The mechanical action in washing machines. MA-test pieces instruction and application &quot; (1982). Set the washing water volume of the full-automatic washing machine (Toshiba, AW-D802VP) to 45 L, and put four cotton T-shirts of the same type with the above-mentioned MA test cloth and six cotton T-shirts of the same type without the stitched MA test cloth. (Approximately 2.2 kg). After putting 67.5 g of the detergent composition into the washing machine for 30 minutes and soaking, the washing steps of eight minutes of washing, three minutes of dehydration, two rinses, and six minutes of dehydration were performed. The MA test cloth was directly taken out of the T-shirt without drying, and the open Silk number. (Cloth damage test evaluation method) The average value of the four MA test cloths and the fixed line was obtained. &lt; Preparation of detergent composition &gt; (Preparation Example 1-1) 99474.doc -42- 200540263 Mix 325 kg of water, 200 kg of 50% by weight sodium dodecylbenzenesulfonate aqueous solution, 75 kg of 40 A 2% by weight aqueous solution of sodium oxalate, 50 kg of carbon sivena, 212.5 kg of sodium sulfate, 5 kg of polyethylene glycol, 2.5 kg of CBS-type fluorescent dye, and 100 kg of zeolite were prepared. After the slurry is homogenized, the slurry is spray-dried to obtain a detergent composition. (Comparative Example 1-1)

Table 1 shows the slip properties of the detergent composition obtained in Preparation Example I-1. This is a cleaner composition with a sliding grade of 2. In addition, the aqueous solution in which the detergent composition was dissolved did not exhibit stringiness. (Preparation example 1_2) 325 kg of water, 240 kg of 50% by weight sodium dodecylbenzenesulfonate aqueous solution, 6 kg of alcohol ethoxylate (carbon number: 12, additional E0: average 8 moles ), 75 kg of a 40% by weight aqueous solution of No. 2 sodium silicate, 50 "of sodium carbonate, 186.5 kg of sodium sulfate, 5 kg of polyethylene glycol, 2.5 kg of CBS-type fluorescent dye, and 100 kg Zeolite, after preparing a homogeneous slurry, spray-dried the slurry to obtain a detergent composition. (Comparative Example 1-2) The sliding property of the detergent composition obtained in δ Weekly Preparation Example 1-2 is shown in Table 1. It is a detergent composition of sliding grade: 2. Also, an aqueous solution in which the detergent composition is dissolved does not exhibit stringiness. (Preparation Example 1-3) 465 kg of water and 48 kg of 50% by weight are twelve. Sodium alkylbenzenesulfonate aqueous solution, 135 kg of 40% by weight sodium polyacrylate aqueous solution, 120 kg of sodium carbonate '60 kg of sodium sulfite, 9 kg of sodium sulfite, 3 kg of CBS-type fluorescent dye with 99474.doc -43- 200540263. The slurry was spray-dried, and 300 kg of zeolite was obtained to obtain a homogeneous slurry to obtain reference particles. 1 part of ηΛ100 at 0 position and 15 parts by weight of alcohol ethoxylate (carbon number: 12, additional EO: flat about 6 mol), 15 parts by weight of sodium alkylbenzenesulfonate, 1 part of polyethylene glycol A mixed solution containing 3 parts by weight of severe burn injury and water was obtained to obtain a detergent composition. (Comparative Example 1-3)

The slip properties of the π detergent composition obtained in Preparation Examples 1 to 3 are shown in Table 1 as a detergent composition with slip grade of 2. In addition, the aqueous solution in which the detergent composition was dissolved did not exhibit stringiness. (Example 1-1) The detergent composition 4. () kg obtained in Preparation Example W was thrown into a concrete mixer (Koyo Machine, manufactured by Industry Co., Ltd., with a capacity of 40 liters), followed by the average molecular weight added 5 million sodium polyacrylate (produced by Toa Synthetic Co., Ltd., AΓ〇η A-20 P ", with drawability), 2 g of DM-type fluorescent dye (made by Chiba-Geigy, Chinopearl DMA), and 12 g of spice tincture at an angle of 30. Mix at a rotation number of 20 r / m for three minutes to obtain a detergent composition containing a surface molecule organic polymer. The washing water in which the detergent composition is dissolved is viscous, and a lubricating layer containing a polymer can be felt on the surface of the T-shirt used. Table 1 shows the slip properties of the obtained detergent composition. Sliding level is 4. In addition, an aqueous solution obtained by dissolving 15 g of the detergent composition in% μ water exhibited stringiness. (Example 1-2) 40 kg of the detergent composition obtained in Preparation Example 1_1 was put into a concrete mix 99474.doc • 44- 200540263 Kishiki (manufactured by Koyo Machinery Industry Co., Ltd., with a capacity of 40 L), and then added Sodium polyacrylate with an average molecular weight of 2 million (manufactured by Toa Kosei Co., Ltd., "Aron A-20P" has stringiness), and 200 g of carboxymethyl cellulose (Nippon, Honda Paper Chemical Co., Ltd. Production: F1GMC), 84 g of sodium percarbonate-containing particles (the bleach particles disclosed in paragraph 00M of Japanese Patent Laid-Open No. 2000 · 256699), 4 g of cellulase (multi-effect cellulase production Granules, Novi = manufactured by the company) and 12g of fragrance, mixed for three minutes at an inclination angle of 3,000 and a rotation number of 20r / m to obtain # a high-molecular organic polymer-containing detergent combination exposed. The detergent liquid dissolving the detergent composition was thick and the polymer-containing lubricating layer was clearly felt on the surface of the T-shirt used. The slip properties of the obtained detergent composition are shown in Table 丨. Sliding level is 5. Also, 15 g of the detergent composition was dissolved in% ... water, and the aqueous solution 'was drawn. (Example 1-3) 40 kg of the detergent composition obtained in Withering Example 1-3 was put into a concrete mixing machine (manufactured by Koyo Machinery Industry Co., Ltd., with a capacity of 40 L), followed by adding an average of 200 g Sodium polyacrylate with a molecular weight of 3 million (with drawing properties), 160 g of methyl methyl cellulose (manufactured by Nippon Paper Chemical Co., Ltd .: F10MC), 8 g of protease (enzymatic granulation for bleaching, manufactured by Novozymes), 4 g of fluorescent dye (produced by iba Geigy, Chinopearl CBS-X) and 16 g of perfume at an inclination angle of 30. 3. Spin at 20 r / m for three minutes to obtain a detergent composition containing organic polymers with the same knife. The washing and dissolving water in which the detergent composition is dissolved is sticky, and the surface of the T-shirt used can clearly feel the lubricating layer of β t substance. The obtained detergent composition was slipped 99474.doc -45-200540263 and 15 g of the detergent composition was drawn. Mobility is shown in Table 1. Sliding level is 4. Aqueous solution obtained by dissolving the compound in 86 ml of water (Examples 1-4) 40 kg of the detergent composition obtained in the preparation process was put into a concrete mixer (manufactured by Koyo Machinery Industry Co., Ltd., capacity 4GL), and Sodium Acrylic Acid / Promethazine Methyl Propionate Sodium Copolymer (AA / AMPS) with an average molecular weight of 10,000 yuan ("Ann A-50P" manufactured by Toa Synthetic Chemical Co., Ltd., with stringiness), 120% methyl cellulose (manufactured by Nippon Paper Chemical Co., Ltd .: F10MC), 4 g of cellulase (multi-effect cellulase granules, manufactured by Novozymes), 8 § protease (pelletizing enzyme granulation (Manufactured by Novozymes) and 16 g of spices at an inclination angle of 30. 2. Mix for three minutes at a rotation speed of 1 / m to obtain a detergent composition containing a high molecular organic polymer. The washing water that dissolves the clean and clean composition is sticky, and a lubricating layer containing a polymer can be clearly felt on the surface of the used t-shirt. The cleanness table of the obtained detergent composition is shown in Table 1-1. The mobility grade is again, and 15 g of the detergent composition is dissolved in an aqueous solution such as 86, which exhibits stringiness. / (Examples 1 to 5) j. 40 kg of the detergent composition obtained in Preparation Example M was put into a concrete mixer (manufactured by Koyo Machinery Industry Co., Ltd., with a capacity of 40 L), and then the average molecular weight was determined to be 280. Wanzhi Polyethylene Oxide (PE〇) (Sumitomo Seiki: 2; manufactured "PEO-8Z", with drawability), 60 g of Slow Methyl Fiber Paper Chemical Co., Ltd .: 48 g Sodium percarbonate-containing particles (disclosed in paragraph 2 of Japanese Patent Laid-Open No. 2_.256699, No. 99474.doc -46- 200540263

White agent particles), 20 g of sodium dodecyloxybenzenesulfonate granules (the bleach activator particles disclosed in paragraph 0018 of Japanese Patent Laid-Open No. 2000-256699), 8 g of cellulose Enzyme (multi-effect cellulase granules, manufactured by Novozymes) and 6 g of fluorescent dye (Chiba-Geigy, Chlnopearl CBS-X) at a tilt angle of 30. 2. The number of revolutions is 20, and the melon is mixed for three minutes to obtain a detergent composition containing an organic polymer of amidine. The washing water that dissolves the detergent composition is viscous, and a lubricating layer containing a polymer can be clearly felt on the surface of the used t-shirt. Table 1 shows the slip properties of the obtained detergent composition. Sliding level is 5. The aqueous solution obtained by dissolving H g of the detergent composition in 86 mi of water exhibited stringiness. (Example 1-6) 4.0 kg of the detergent composition obtained in Preparation Example I-1 was put into a concrete mixer (manufactured by Koyo Machinery Industry Co., Ltd., with a capacity of 40 L), and then an average molecular weight of 48 g was added to 4.5 million polyethylene oxides ("PEO-18Z" manufactured by Sumitomo Refinery Co., Ltd. with stringiness), 2 g of fluorescent dyes (manufactured by Chiba-Geigy &amp; Chinopearl CBS-X), and 12 g of The fragrance is mixed at an inclination angle of 30 ° and a rotation number of 20 r / m for three minutes to obtain a detergent composition containing a high molecular organic polymer. The washing water in which the detergent composition is dissolved is viscous, and a lubricant layer containing a polymer is clearly felt on the surface of the T-shirt used. Table 1 shows the slip properties of the obtained detergent composition. Sliding level is 5. In addition, an aqueous solution obtained by dissolving 15 g of the detergent composition in 86 ⑹ of water exhibited stringiness. (Example 1-7) 99474.doc -47- 200540263 Put the 4.0 kg of the detergent composition obtained in Preparation Example 1-2 into a concrete mixer (manufactured by Koyo Machinery Industry Co., Ltd., with a capacity of 40 liters), Next, 280 g of polypropylammonium (with drawing properties) with an average molecular weight of 5 million, g of methyl cellulose (made by Nippon Paper Chemical Co., Ltd. · F10 MC), and 16 g of fragrance were added at an inclination angle of 30 . Mix at a rotation number of 20 r / m for three minutes to obtain a detergent composition containing a high molecular organic polymer. The washing water in which the detergent composition was dissolved was viscous, and a lubricant layer containing a polymer was clearly felt on the surface of the τ-shirt used. Table 1 shows the slip properties of the obtained detergent composition. Sliding level is 4. Also, an aqueous solution obtained by dissolving 5 g of the detergent composition in 86 ml of water exhibited a stringiness. In addition, when the hand washing was performed in Examples 1-1 to 1-7, no cracks in the hands or damage to the fibers occurred. Using the detergent composition obtained in Preparation Example 1.1 and Example W, the above-mentioned clothing damage test was performed. The number of open threads (average of the four MA test cloths) was 86 and 70, respectively. 99474.doc -48 200540263%

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SO ed (booth 00SAVW) sdwv / w (booth 08 (NAVso3d (booth 0S inch AVWoHd (booth 00SAVN)) wall love bismuth. ¥ 屮 令 ^ 屮 长 01 ^-佘 峒 面 佐 &lt; ¥ & ΝΝφ ^^ ν -δ- ^ inch 1mm 1 S 1 1mm τ ^ ~~ _ ~~~ — — — — — — — — ihi 99474.doc -49- 200540263 &lt; Synthesis of Polymers> Synthesis Example II-1: Synthesis Example of Polymer 丨 [2_Acrylamidine_2_Sodium Methyl Propane Sulfonate Homopolymer] 50.3 g of 2-acrylamido-2-methyl Sodium propane sulfonate, 32.4 g of sodium hydroxide, 3.95 g of 2,2'-azobis (2-methylpropionamidine) dihydrochloride (ν · 50), Wako Pure Chemical Industries ( (Manufactured)) dissolved in 135 g of ion-exchanged water, and heated to 5 (TC and stirred for one hour under a nitrogen environment. After that, it was stirred for eight hours after being upgraded to 70 C. Diluted with 360 g of ion-exchanged water Then, it was added to 2700 g of ethanol, and the precipitated solid polymer was dried under reduced pressure to obtain 55.0 g of a colorless solid polymer (yield: 98 8%). The GPC measurement result of the obtained polymer showed a peak Top molecular weight is 2 million (PEO equivalent, column · G MPWXL + GMpwxL, development solvent · 0.2 M phosphate buffer / CH3CN = 9/1 (weight ratio), concentration: 0.05 mg / m] L, flow rate: 0.5 mL / min, 4 (TC, detection Device: rALls, the average molecular weight was measured under the same conditions as described below. ^ Synthesis Example Η · 2 · Polymer 2 [2-Propanylamine-2-Hydroxypropionate Sodium Homopolymer] Synthesis Example 1 〇g of sugar ester (S-770, Mitsubishi Chemical Foods Co., Ltd.) is dissolved to 185 g of η-hexane, and 2-propane 2-propylene in 50 g of ion-exchanged water is dissolved therein. Pyridamine-2-methylpropylpropionate, sodium hydroxide (3.86 g), and ammonium persulfate (0.055 g) were dispersed, and the temperature was raised to nitrogen and stirred for two hours in a nitrogen environment. The aqueous phase was separated, cooled down to a water content of 30 wt%, and the obtained solid particles were dried under reduced pressure to obtain 22.0 g of a colorless granular polymer (yield: 99.1%). The obtained polymerization was 99474 .doc -50- 200540263 The results of GPC measurement showed that the peak molecular weight was 3 million and the average particle size was 230 μm.

The average particle diameter was determined using a sieve specified in JIS Z 8801. Ten sections of sieves and trays with openings of 2000 μm, 1400 μm, 1000 μm, 710 μm, 500 μm, 355 μm, 250 μm, 1 80 μm, 125 μm, and 106 μm are installed on a rotating machine (made by HEIKO SEISAKUSHO) After 100 g of sample was shaken for ten minutes (tap: 156 times / minute, rotation: 290 times / minute), the weight of particles remaining on the receiving pan and each sieve was measured. (From the fine powder side) Set the opening of the sieve with a cumulative weight ratio of 50% or more as a μιη, and set the opening of a sieve larger than a μπι as b μιη, and accumulate the weight ratio of the sieve from the tray to a μηι When it is set to c% and the weight ratio on the sieve of a μm is set to d%,

(Average particle diameter) = 10A Calculated based on A = (50- (c-d / (10g b-log a) xlog b)) / (d / (10g b-log a)). Synthesis Example II-3: Synthesis Example of Polymer 3 [Homopolymer of 2-acrylamido-2-methylpropanesulfonate sodium] 6.0 g of sugar ester (S-770, Mitsubishi Chemical Foods (Strain)) After dissolving in 950 g of η-hexane and refluxing under a nitrogen environment, it took one hour to dissolve 665 g of 2-propanolamine methylpropanesulfonic acid dissolved in 590 g of ion-exchanged water. Sodium, 0.80 g of 2,2, -azobis (2-methylpropionamidine) dihydrochloride (V-50, Wako Pure Chemical Industries (manufactured)) dripped really dispersed, and then stirred three ten minutes. After azeotropic dehydration / drying in the same manner as in Synthesis Example 11_2 ', 664 g of a colorless granular polymer was obtained (yield: 99.8%). As a result of GPC measurement of the obtained compound I, the peak top molecular weight was 6.2 million. The average particle diameter was 250 Pm. Moreover, the stringiness was confirmed in 4% by weight of an aqueous solution of the polymer. 99474.doc -51-200540263 Synthesis Example II-4: Synthesis Example of Polymer 4 [Copolymer of 2-acrylamido-2-methylpropanesulfonate / sodium acrylate = 95: 5 (molar ratio)] Dissolve 6.00 g of sugar ester (S-770, Mitsubishi Chemical Foods Co., Ltd.) in 800 g of cyclohexane and raise the temperature to 70 ° C under a nitrogen environment, while taking one hour to dissolve in 510 g of ions 600 g of sodium 2-acrylamidomethylpropanesulfonate, 160 g of sodium hydroxide, 10 g of acrylic acid, 2.40 g of 2,2'-azobis (2-methyl (III) Dihydrochloride (v-50, manufactured by Wako Pure Chemical Industries, Ltd.) was dropped and dispersed, and stirred for 30 minutes. After azeotropic dehydration / drying in the same manner as in Synthesis Example Π-2, 672 g of a colorless granular polymer was obtained (yield: 99.4%). As a result of GPC measurement of the obtained polymer, the peak top molecular weight was 4.5 million. The average particle size was 150 μm. Moreover, stringability was confirmed in a 1.0% by weight aqueous solution of the polymer. Synthesis Example II-5: Synthesis Example of Polymer 5 [2-acrylamido-2-sodium methylpropane sulfonate / sodium acrylate = 95: 5 (mole ratio) copolymer] A synthesis example of 6.00 g of a sugar ester ( 8.77, Mitsubishi Chemical Foods Co., Ltd.) was dissolved in 800-hydroxy n-hexane and refluxed under a nitrogen environment while maintaining it at 〇. 〇 Below and taking hours to dissolve / dissolve in 510 g of ion-exchanged water, 600-§ 2_acrylamido_ sodium 2-methylpropane sulfonate, 160 g of sodium hydroxide, 10 g of acrylic acid 0.82 g of 2,2'-azobis (2-methylpropionamidine) dihydrochloride (ν · 50, manufactured by Wako Pure Chemical Industries, Ltd.) was dropped and dispersed, followed by stirring for 30 minutes. After azeotropic dehydration / drying in the same manner as in Synthesis Example II-2, 674 g (99.7 / 0) of a colorless granular polymer was obtained. Ο? Of the obtained polymer. As a result of measurement, the peak top molecular weight was 780,000. The average particle size was 22 pm. Moreover, stringability was confirmed in a 1.0% by weight aqueous solution of the polymer. 99474.doc -52- 200540263 Synthesis example II-6: Synthesis example of polymer 6 [2-acrylamido-2-methylpropanesulfonic acid cross-linked polymer]

2,000 g of sugar ester (S-77, Mitsubishi Chemical Foods Co., Ltd.) was dissolved in 950 g of t-hexane and refluxed under a nitrogen environment, and it took one hour to dissolve in 390 g of ion-exchanged water. 44 g of sodium 2-acrylamido-2-methylpropanesulfonate, 0.011 g of polyethylene glycol dimethacrylate (NK ester 23 G, Shin Nakamura Chemical Industry Co., Ltd.), 0.5 0 g of 2,2, -azobis (2.methylpropionamidine) dihydrochloride (V-50, manufactured by Wako Pure Chemical Industries, Ltd.) was dropped and dispersed, and further mixed for 30 minutes. Take and synthesize example! After azeotropic dehydration / drying in the same manner, 438 g (yield: 99.5%) of a colorless granular polymer was obtained. As a result of GPC measurement of the obtained polymer, the peak top molecular weight was 5 million. The average particle size was 200 μm. Moreover, the drawability was confirmed in an aqueous solution of the polymer ι · 〇 by weight. &lt; Preparation of detergent composition &gt; (Preparation Example 1-1-1) 325 kg of water, 200 kg of 50% by weight sodium dodecyl benzoate aqueous solution, and 125 kg of 40% by weight of silicon No. 2 were mixed. Aqueous sodium solution, 50 kg of sodium carbonate, 50 kg of sodium tripolyphosphate, 150 kg of sodium sulfate, 5 kg of polyethylene glycol, 6.25 kg of a 40% by weight aqueous solution of acrylic acid / maleic acid copolymer, 2.5 kg of CBS-type fluorescent dye and 100 kg of zeolite to prepare a homogeneous slurry, and spray-dried the slurry to obtain a detergent composition. The physical properties of the obtained detergent composition were evaluated according to a method not described. &lt; Evaluation method of hand washing and washing &gt; The test was performed in the same manner as described above, and the average value of 99474.doc -53- 200540263 evaluated by six professionals was set as a grade. &lt; Fabric damage test evaluation method &gt; The test was performed in the same manner as described above, and the average value of the four MA test cloths was obtained. &lt; Evaluation method of prevention of carbon re-pollution &gt; 5.0 g of the detergent composition was dissolved in 4,000 cc of water (CaCly 55.42 mg / L, MgCl2.6H2: 43.51 mg / L) . Followed by

Carbon black selected by the Japan Oil Chemical Society (preferably manufactured by Asahi Carbon Co., Ltd., Asahi Washing Carbon Black) was added thereto, and the carbon black was uniformly dispersed by irradiating ultrasonic waves of 26 to 15 kHz for five minutes. Next, move it to the sample cup of a hybrid detergency tester (Terg_0_Tometer) under 20 ° C and place five 6 cm x 6 cm cotton white cloths The standard selected by the Chemical Society was washed with # 2023 cloth sold by the Scientific Association) and stirred at a rotation speed of 100 ± 5 r / m for ten minutes. Next, take out the cotton cloth, twist it gently so that the moisture content becomes 200% by weight or less, and then put 4 (rc of 1000 mL of water (CaCl2: 55.42 mg / L, MgCl2.6H20: 43.51 mg / L). ), Use a hybrid cleaning force tester (rotating speed 100 ± 5 r / m) for three minutes, and operate the washing twice. Then, the white cloth taken out is air-dried and ironed to measure the reflectance at 550 nm. (Nippon Denshoku Industries (manufactured) color measurement colorimeter). The recontamination prevention rate was calculated from the following formula and evaluated on the basis of the following criteria. The recontamination prevention rate (%) = [(Reflection of cotton white cloth after the test) Rate) / (reflectivity of cotton white cloth before test)] XI 〇〇Evaluation standard 0 · Repollution prevention rate is 60% or more X · Repollution prevention rate is less than 60% 99474.doc -54- 200540263 &lt; mud Repollution prevention evaluation method>

5.0 g of the detergent composition was dissolved in 1000 mL of used water (CaCl2: 55.42 mg / L, MgCl2.6H2 ·· 43.51 mg / L) at 40 ° C. Next, 2.5 g of mud (Kanuma red clay for horticulture passed through a 200-mesh sieve [purchased from Kuniyukien (Kyoto Co., Ltd., Osaka Prefecture and Shinzen-cho, Sakai-shi)) was added thereto, and dispersed uniformly. Next, 20 ° Move it to the sample cup of the hybrid detergency tester (detergent tester: Terg-0-Tometer) under C, and put five pieces of 6 cm &gt; &lt; 6 cm cotton white cloth Standards selected by the Association, # 2023 cloth sold by the Washing Science Association) Stir for ten minutes at a rotation speed of 100 ± 5 r / m. Then take out the white cotton cloth and gently twist it so that the moisture content becomes 200% by weight or less. , Put in 1000 mL of water (CaCl2: 55.42 mg / L, MgCl2.6H20: 43.51 mg / L) at 40 ° C, and wash with a hybrid washing force tester (rotation speed 100 soil 5 r / m) The washing was performed twice and then the white cloth was taken out. The white cloth taken out was air-dried and ironed, and the reflectance of 46nm * (color measurement colorimeter manufactured by Nippon Denshoku Industries Co., Ltd.) was measured. The pollution prevention rate is evaluated on the basis of the following. Recontamination prevention rate (%) = [(Reverse of cotton white cloth after test Rate) / (Reflectivity of cotton white cloth before test)] XI 00 Evaluation criteria 0: Recontamination prevention rate is 66% or more x: Recontamination prevention rate is less than 66% (Comparative Example II-1) Modification Example II- The slippage and re-pollution prevention table of the detergent composition obtained in 1 is shown in Table 2. The combination of its minerality # grade is 2, the carbon re-pollution prevention is 0, and the mud re-pollution prevention is 0. 99474.doc -55- 200540263 (Preparation Example II-2) 325 kg of water, 240 kg of 50% by weight sodium dodecylbenzenesulfonate aqueous solution, 6 kg of alcohol ethoxylate (carbon number · 12, additional EO: average 8 mol), 75 kg of 40 wt./0 No. 2 sodium silicate aqueous solution, 50 kg of sodium carbonate, 186.5 kg of sodium sulfate, 5 kg of polyethylene glycol, 2.5 kg of CBS-type fluorescent dye and 100 kg of zeolite to prepare a homogeneous slurry, and spray-dried the slurry to obtain a detergent composition. (Comparative Example II-2) The detergent composition obtained in Preparation Example II-2 The sliding properties and re-pollution prevention properties are shown in Table 2. It is a cleaning agent with a sliding grade of 2, a carbon re-pollution prevention property of 0, and a mud re-pollution prevention property of 0. Compound. (Preparation Example II-3)

Mix 465 kg of water and 50 kg of 48 kg. /. Dodecyl benzoate sodium benzoate solution, 135 kg of 40% by weight sodium polyacrylate solution, 120 kg of sodium lactate, 60 kg of sodium sulfate, 9 kg of sodium sulfite, 3 kg of CBS ^ type fluorescent Light dye and 300 zeolite to obtain a homogeneous slurry. The slurry was spray-dried to obtain reference particles.

A detergent composition is obtained. (Comparative Example II-3)

Preventive expression is not silk 2. It is a cleaner composition with a sliding grade of 10 grades, sliding properties and re-pollution, ′ carbon re-pollution prevention 99474.doc -56-200540263 is 0, and mud re-pollution prevention is ◦. (Example 11_1)

4.0 kg of the detergent composition obtained in Preparation Example II-2 was put into a concrete mixer (manufactured by Koyo Machinery Industry Co., Ltd., with a capacity of 40 L), and then 72Og of polymer 1 of Synthesis Example II_1 was added. 2 g of DM-type fluorescent dye (Chinopearl DMA, manufactured by Chiba-Geigy, Inc.) and 12 g of perfume were mixed at an inclination angle of 30 ° and a rotation number of 20 r / m for three minutes to obtain a detergent composition. Table 2 shows the slip properties and re-pollution prevention properties of the obtained detergent composition. Its sliding property rating was 4, carbon re-pollution prevention was 0, and mud re-pollution prevention was 0. (Example II-2) The 4.0 kg of the detergent composition obtained in Preparation Example II-3 was put into a concrete mixer (manufactured by Koyo Machinery Industry Co., Ltd., with a capacity of 40 L), followed by the addition of 36 g of synthetic The polymer of Example II-2, 200 g of carboxymethyl cellulose (manufactured by Nippon Paper Chemical Co., Ltd .: F10MC), and 84 g of sodium percarbonate-containing particles (disclosed in Japanese Patent Laid-Open No. 2000-256699) The bleach particles of paragraph 0019), 4 g of cellulase (multi-effect cellulase granules, manufactured by Novozymes), and 12 g of perfume, at an inclination angle of 30. 3. Mix for three minutes at a rotation number of 20 r / m to obtain a detergent composition. Table 2 shows the sliding properties and re-pollution prevention properties of the obtained detergent composition. Its sliding property rating was 4, carbon re-pollution prevention was 0, and mud re-pollution prevention was 0. (Example II-3) 40 kg of the detergent composition obtained in Preparation Example II-1 was put into a concrete mixer (manufactured by Koyo Machinery Industry Co., Ltd., with a capacity of 40 L), and then 99474.doc -57- 200540263 120 g of Synthetic Example π-3 polymer 3, 160 g of carboxymethyl cellulose (F10MC, manufactured by Nippon Paper Chemical Co., Ltd.), 8 § protease (enzymatic granulate for bleaching, Novozymes (Manufactured), 4 g of fluorescent dye (Chinopearl CBS-X manufactured by Chiba_Geigy, Inc.), and 16 g of perfume, mixed at a tilt angle of 300 and a rotation number of 20 r / m for three minutes to obtain a detergent composition. Table 2 shows the sliding properties and re-pollution prevention properties of the obtained detergent composition. Its sliding property rating was 5, carbon re-pollution prevention was 0, and mud re-pollution prevention was 0. (Example II-4) 40 kg of the detergent composition obtained in Preparation Example 11_2 was put into a concrete mixer (manufactured by Koyo Machinery Industry Co., Ltd., with a capacity of 40 L), and then 32 g of Synthesis Example II- 4 polymer 4, 48 g of sodium percarbonate-containing particles (the bleach particles disclosed in paragraph 019 of Japanese Patent Laid-Open No. 2000-256699), 20 g of dodecane oxygen Sodium benzenesulfonate granules (the bleach activator particles disclosed in paragraph 0018 of Japanese Patent Laid-Open No. 2000-256699) 120 g of slow methyl cellulose (manufactured by Nippon Paper Chemical Co., Ltd. · F10MC) , 4 g of cellulase (multi-effect cellulase granules, manufactured by Novozymes 1) 8 g of protein conversion (enzymatic granules for bleaching, manufactured by Novozymes) and 16 g of perfume, to tilt Angle 30. 2. Turn the number 20 &quot; melon for three minutes to obtain a detergent-containing composition. Table 2 shows the β-resistance of the resulting cleaner composition. Its sliding property rating was 5, carbon re-pollution prevention was 0, and mud re-pollution prevention was 0. (Example II-5) 40 kg of the detergent composition obtained in Preparation Example IM was put into a concrete mix 99474.doc -58-200540263 Kishiki (manufactured by Koyo Machinery Industry Co., Ltd., with a capacity of 40 L), and then added 60 g of polymer II-5 of Synthesis Example 5, 8 g of cellulase (multi-effect cellulase granulate, manufactured by Novozymes), 6 g of fluorescent dye (manufactured by Chiba Geigy, Chin) pearl CBS_X) and 12 g of perfume were mixed at an inclination angle of 30 ° and a rotation number of 20 r / m for three minutes to obtain a detergent composition. The sliding properties and re-pollution prevention properties of the obtained detergent composition are shown in Table 2 /, /, the dynamic net grade is 5, the carbon re-pollution prevention property is 0, and the mud re-pollution prevention property is 0. (Example II-6) 40 kg of the detergent composition obtained in Preparation Example II-1 was put into a concrete mixer (manufactured by Koyo Machinery Industry Co., Ltd., with a capacity of 40 L), and then 160 g of a synthesis example was added. The polymer 6 of 11_6 and the fragrance of 12 g were mixed for three minutes at an inclination angle of 300 and a square revolution of 20 r / m to obtain a detergent composition. Table 2 shows the slip properties and re-pollution prevention properties of the obtained detergent composition. Its sliding property rating was 5, carbon re-pollution prevention was 0, and mud re-pollution prevention was 0. Compared with the case of Comparative Example IlqqU, the washing performed with the detergent composition obtained in Examples II-1 to Π_6 can reduce the unpleasant factors of so-called "roughness", "friction", or physical fatigue, The difference can thus be clearly felt. Moreover, in the washing performed in Examples H-1 to Π-6, no cracks in the hands or deformation of the washings were generated. The above cleaning damage n 4 test was carried out using the cleaning agent composition of Preparation Example 1 and Examples 11-5. The number of open threads (average of the four MA test cloths) was 88 and 72, respectively. 99474.doc -59- 200540263% (N 9 丨 11 odol ε · 0 〇 · inch 〇 s

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QlodI 2 d, 0001 τ τ τ 〇Q, ss ^ CNI-IIi # Bismuth on UWU) i ^ s spectrum φ ^ Real 溆屮 &lt; ^ ir71r) sdsv (N # &lt; n ^^^

(§ (NIS (Stall 0S inchΪ 屮 &lt; ^ irTlr) vv / saHwv inch life Bismuth φ (minus 081 &gt; 驷 屮 令 霄 牛) w / sdsv S # ^ S4 ^^ 砩 Η? 鞔 藏 赛姝 ± 1, «boat siT ^ ^ ^ ΐ 99474.doc -60- 200540263 The cleaning agent composition of the present invention is particularly suitable for hand washing. Therefore, as for the present invention described, it is clear that the same can be borrowed. It can be changed by various methods. It can be considered that the relevant changes are not deviated from the purpose and scope of the present invention, and the industry should be aware that such changes are included in the scope of the patent application below. 99474.doc -61-

Claims (1)

200540263 10. Scope of patent application: 1_: A method for improving the sliding property of the cleansing liquid in the washing liquid. The method is to make the organic polymer having a stringiness in the washing liquid during the washing. 2. —A method for improving the sliding property of the object to be washed in a hand-washing lotion, which involves the presence of a stringy organic polymer in the lotion when the hand-washing lotion is used. 3. A hand washing and washing method, which comprises the step of washing and filling the object to be washed with a washing liquid by hand. The above washing liquid is a washing liquid containing a stringy organic polymer showing a stringing property, or the washing water is diluted to Washing liquid made from more than 1000 times. 4. The method of hand washing and washing according to item 3, wherein the pH of the washing liquid is above 90. A detergent composition containing a stringy organic polymer having an average molecular weight of more than 0.01% by weight of 15 million or more. The detergent composition according to claim 5, comprising: ⑷ more than G.1% by weight of a stringable organic polymer having an average molecular weight of ⑽10,000 or more, (b) a surfactant, (c) a test agent, And (d) metal ion blocking agents. 7. The detergent composition according to item 5, which is in a powder or granular form. 8 · A cleansing composition according to any one of # seeking items 5 to 7, the towel further containing an inorganic salt of hydrogen peroxide in water, the content of the inorganic salt is 15 99474.doc 200540263 9 · a The laundry detergent composition contains 60 mols of monomers having an average molecular weight of 500,000 or more. The above are polymers having a continuous acid group or a salt type group thereof, a sulfuric acid group or a salt type group thereof. 10. The laundry detergent composition according to claim 9, which is in a powder or granular form. 11 · The cleaning agent composition for clothing as described in item 9 above, which contains (a) an average of 5G million or more per 7 square meters ^ 6 () mole% or more of the constituent monomers have a continuous acid group or a salt form thereof (B) a surfactant, (b) a testing agent, and (d) a metal ion blocking agent. 12. The cleaner composition for clothing according to any one of items 9 to 11, wherein the single system in the basin is derived from a group selected from 2-propanolamine · 2 · methylpropyl: its salt, styrene A group of one or more monomers of sulfonic acid and its salts. 13. A slip improver containing a stringy organic polymer having an average molecular weight of more than 1.5 million by weight in excess of Qi. For example, the slip improver of claim 13, wherein the organic polymer is a polymer or copolymer, a polysaccharide or a polypeptide having a sugar skeleton, and the above polymer or 14.15 copolymer is derived from an epoxy resin selected from G Shen, acrylic acid, acrylamide, acrylamide methylpropane sulfonic acid, dimethyl beauty face II-based ethyl methacrylic acid, ethyl alcohol, and monomers composed of these mixtures. A slip improver containing an average molecular weight of 500,000 or more and 60 mol% or more of a constituent monomer being a polymer having a material group or a salt type group thereof, sulfur 99474.doc 200540263 acid group or a salt type group thereof Thing. 16. The slip improver according to claim 15, wherein the constituent monosystem is selected from the group consisting of 2-acrylamidine, 2-methylpropane, and its salt, styrene acid, and its salt. 17. One or more kinds of one or more monomers. Washing method using a detergent composition of χ 7 inch as claimed in item 9. Method 0. Method 18. Washing using a slipping improver as claimed in item 15. 99474.doc 200540263 VII. Designated Representatives: (1) The designated representative of this case is: (none) (2) The component symbols of this representative are simply explained: 8. If there is a chemical formula in this case, please disclose the ones that can best show the characteristics of the invention. Chemical formula: (none) 99474.doc